Process for producing acyloxydodecatrienes

ABSTRACT

Acyloxydodecatriene is produced by reacting an octatriene, a butadiene and a carboxylic acid in the presence of a catalytic amount of a divalent palladium compound selected from the group consisting of organic acid salts of palladium (II), chelate complexes of palladium (II) and palladium nitrate.

United States Patent [1 1 Hattori et a1.

PROCESS FOR PRODUCING ACYLOXYDODECATRIENES Inventors:

Assignee:

Filed:

Appl. No.:

Saburo Hattori, Tokyo; Naoshi Imaki, Kawasaki, both of Japan Mitsubishi Chemical Industries, Ltd., Marunouchi, Cheyoda-ku, Tokyo, Japan Dec. 27, 1971 Foreign Application Priority Data Dec. 30, 1970 Japan 45-125874 Mar. 29, 1971 Japan 46-18561 US. Cl. 260/497 A, 260/468 R, 260/476 R int. Cl. co7 67/04 Field of Search ..260/497 A, 476 R, 468 R, 2 6 RLiLQ-QN References Cited UNITED STATES PATENTS Wilke 260/677 R Jan. 29, 1974 Primary Examiner--Lorraine A. Weinberger Assistant Examiner-Richard D. Kelly Attorney, Agent, or Firm--Norman F. Oblon et al.

[5 7] ABSTRACT Acyloxydodecatriene is produced by reacting an octat snes rbu ad g and afi bq sy cis i s P ence of a catalytic amount of a divalent palladium compound selected from the group consisting of organic acid salts of palladium (lI), chelate complexes of palladium (II) and palladium nitrate.

10 Claims, No Drawings PROCESS FOR PRODUCING ACYLOXYDODECATRIENES RELATED APPLICATION This application is related in subject matter to copending US. Pat. application Ser. No. 207,649, filed Dec. 13, 1971, of the same title and by the same inventors.

BACKGROUND OF THE INVENTION 1. Field Of The Invention This invention relates generally to a process for producing acyloxydodecatrienes. More particularly, this invention relates to a process for producing acyloxydodecatrienes by the use of octatriene, butadiene and a carboxylic acid as the reactants.

In this specification, the term butadiene is intended to include both l,3-butadiene and the lower alkyl substituted 1,3-butadienes, and the term octatriene is intended to include both 1,3,7-octatriene and the lower alkyl substituted l,3,7-octatrienes, which are substituted on the 2 8 carbon atom positions.

2. Description Of The Prior Art Acyloxydodecatrienes are well known triene derivatives which have found important industrial utilization in a variety of fields. In studying the oligomerization reactions of butadiene, it had been found that the reaction of butadiene, carboxylic acid and octatriene can be quite effectively catalyzed by the use of certain palladium compounds.

SUMMARY OF THE INVENTION Accordingly, it is one object of this invention to provide a process for producing useful acyloxydodecatrienes in an industrially effective manner.

This and other objects of this invention, as will hereinafter become more readily apparent, can be attained by reacting an octatriene, a butadiene, and a carboxylic acid in the presence of a catalytic amount of a divalent palladium compound selected from the group consisting of organic acid salts of palladium (II), chelate complexes of palladium (II) and palladium nitrate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The octatriene used as a reactant herein may be 1,3,7-octatriene or a lower alkyl substituted 1,3,7- octatriene having lower alkyl groups at the 2 8 positions and preferably at the 2 7 position. It is especially preferable to use an octatriene having the formula:

CH C CH=CHCH CH -C =CH 1 wherein each R, may be the same or different, and each may represent hydrogen or an alkyl group. Suitable examples of said formula I include 1,3,7-octatriene, 2,7- dimethyl-l ,3,7-octatriene, etc.

The carboxylic acids used as reactants in this process are those compounds having the formula:

R, CO H wherein R represents an alkyl group, cycloalkyl group, aryl group or aralkyl group and which contains two to 20 carbon atoms. Suitable examples of compounds having the formula II include the aliphatic carboxylic acids, e.g., acetic acid, propionic acid, lactic acid, isolactic acid, pivalic acid; alicyclic carboxylic acids, e.g., cyclohexyl carboxylic acid; and aromatic carboxylic acid, e.g., benzoic acid. It is most preferable to use a lower aliphatic carboxylic acid, e.g., acetic acid and propionic acid, and especially acetic acid.

The reaction of this invention can be shown by the following schematic, when the compound having the formula I is used as the octatriene:

In the reaction of this invention, acyloxyoctadicncs having the following formulae (IV, V and VI) are produced as byproducts:

cu, Cl-l--CH CH -Cl-I Cl-l= cncu ocon CH =Cl-ICH -CH CH CHCH=CH ocoR v) CH CH=CI-l-Cl-I CH -CHCH=CH 40 OCOR (VI) The catalysts used for the process of this invention are divalent palladium compounds selected from the group consisting of organic acid salts of palladium (II), chelate complexes of palladium (II) and palladium nitrate. The organic acid salts of palladium (II) can be divalent palladium carboxylate, such as palladium acetate, palladium propionate, palladium benzoate, or the like. The chelate complexes of palladium (II) can be chelated divalent palladium compounds such as palladium acetylacetonate, palladium acetoacetic ester complex, or the like. The palladium compound may be used in amounts of l X 10 1.0 gram atom, preferably l X l0" l X 10* gram atom, as palladium atom per 1 mole of octatriene.

The usable quantitative ratios of the octatriene, the butadiene and the carboxylic acid can be selected over wide ranges. However, the selectivity of the reaction for acyloxydodccatrienes or acyloxyoctadienes will vary depending upon the quantitative ratio of the three reactants. In order to maximize the yield of acyloxydodecatrienes, it is preferable to use a molar ratio of the three reactants of 1.0 0.5 5.0 0.1 1.0 and preferably 1.0 1.0 2.0 0.2 0.5 of octatriene:- butadienezcarboxylic acid. When the molar ratio of butadiene is low, the reaction will be selective toward acyloxydodecatrienes, and higher molar ratios will shift the equilibrium toward acyloxyoctadienes.

When the palladium compound is mixed with certain other additives, such as the phosphines, especially tri phenylphosphine, it has a tendency to decrease the formation of acyloxydodecatrienes. Therefore, the use of such phosphines is not desirable if high yields of acyloxydodecatrienes are desired.

The reaction can be effected without a solvent medium. However, it is possible to use an inert medium. Typical mediums include the aromatic compounds, e.g., benzene, toluene; ethers, e.g., diethylether, tetrahydrofuran, dioxane; esters, e.g., ethyl acetate; ketones, e.g., acetone.

The reaction temperature may be 150C., and preferably 40 120C. The reaction velocity is low at lower temperatures, while byproducts of 4- vinylcyclohexene and dodecatetraene, etc. are produced, and the catalytic activity is decreased at higher temperatures. The reaction pressure may be 1 50 atm., and preferably atm., and the reaction can be carried out under the pressure of an inert gas, e.g., nitrogen or argon.

The reaction mixture may include acyloxydodecatriene, acyloxyoctadiene, unreacted raw materials, medium and catalyst. Following the reaction, the reaction products may be separated and the unreacted reactants recovered by distillation.

An equilibrium relationship exists between the lacyloxydodecatriene and the 3-acyloxydodecatriene in the reaction system. Accordingly, when one type of isomer is supplied to the reaction system, the formation of the same type of isomer will be decreased and the formation of the other type of isomer will be increased. It is therefore desirable to add a 3-acyloxydodecatriene when the formation of a l-acyloxydodecatriene is desired, and to add a l-acyloxydodecatriene when the opposite result is desired. The amount of such isomer which may be added to the reaction is not limited and can be more or less than the equilibrium amount at the particular reaction condition. When the amount of one isomer added to the reaction system is greater than the equilibrium amount, the formation of the same type of the adduct will be decreased, and simultaneously a portion of the isomer added will be isomerized to the opposite type of isomer until equilibrium is reached between the two isomers at the reaction conditions. The desired isomer can therefore be selectively and simply produced in an industrially advantageous manner.

The acyloxydodecatrienes prepared by the process of this invention may be the esters of long chain unsaturated alcohols having a straight chain structure, as stated above, which are useful for producing long chain unsaturated alcohols, long chain unsaturated carboxylic acids, synthetic drying oils and other useful derivatives.

In the process of this invention, an acyloxyoctadiene is produced as a reaction byproduct, but the acyloxyoctadienes can be easily separated from the acyloxydodecatrienes by distillation. Moreover, acyloxyoctadienes can be used as starting materials for the production of a variety of derivatives. Accordingly, the byproduction of acyloxyoctadienes will not cause any severe difficulty.

The main starting material for the process of this invention, the octatrienes, can be easily produced by dimerization of butadiene or isoprene. Accordingly, the process of this invention is quite advantageous from an industrial point of view.

ADT: acyloxydodecatrienes 1 -ADT: l-acyloxy-2,7,1 l-dodecatrienes 3-ADT: 3-acyloxyl ,7,1 l-dodecatrienes AOD: acyloxyoctadienes l-AOD: 1-acyloxy-2,7-octadienes 3-AOD: 3-acyloxyl ,7-octadienes 3'-AOD 3-acyloxy- 1 ,6-octadienes D rate: molar of ADT to total amount of ADT and AOD in the resulting product; percent of l-ADT or l-AOD to ADT or AOD.

1'! rate:

EXAMPLE 1 0.3 m mole of palladium acetate was dissolved in 0.2 mole of 1,3,7-octatriene under an argon atmosphere. This solution and 0.1 mole of acetic acid were charged to a ml. microbomb, which is designed to be shaken in an oil bath. The microbomb was purged with nitrogen gas and 0.2 mole of butadiene was added to the microbomb. The contents were heated to 80C. and the reaction was carried out for 11 hours at said temperature. After the reaction, the microbomb was cooled to room temperature, and unreacted butadiene was recovered and the resulting products were analyzed. The conversion of acetic acid was 71 percent and the resulting products were 4.0 g. of l-acetoxy-2,7- octadiene (l-AOD), 0.9 g. of 3-acetoxy-l,7-octadiene (3-AOD) and 3-acetoxy-l,6-octadiene (3'-AOD) and 6.9 g. of 1-acetoxy-2,7,1 l-dodecatriene (l-ADT), and

2.5 g. of 3-acetoxy-l,7,l l-dodecatriene (3-ADT). Ac- I cordingly, the D rate was 59 percent and the n rate for ADT was 74 percent.

1-acetoxy-2,7,1 1 -dodecatriene and 3-acetoxy- 1,7,1 l-dodecatriene, respectively, having the following characteristics, were found. 1-acetoxy-2,7,1 1- dodecatriene is a colorless liquid having a boiling point of C./l mmHg and the analytical results thereof are as follows:

a. Elementary analysis: C H O C(%) H(%) Calculated 75.63 9.98 Analysis 75.36 9.94

b. Infrared spectra:

absorption bands at 0. Nuclear magnetic resonance spectra:

absorption bands at 4.2-4.7 (multiple lines) 4.7-5.2 (multiple lines) 5.4-5.6 (double lines) 7.8-8.1 (multiple lines) 8.0 (single line) and 8.3-8.6 (multiple lines) of 1 value.

(1. Mass spectra:

peaks at 43 (CH CO), 61 (CH C(OH) and 162 (C H Of M/e value.

Molecular weight is 222 cu cooc n e. Refractive index:

3-acetoxy-1 ,7,1 l-dodecatriene is a colorless liquid having a boiling point of 95 100C./ 1 mmHg and the analytical results thereof are as follows:

a. Elementary analysis: C I-1 5 C Calculated 75.63 9.98 Analysis 75.95 10.04

b. Infrared spectra:

absorption bands at c. Nuclear magnetic resonance spectra absorption bands at 4.0-4.7 (multiple lines),

4.7-5.2 (multiple lines),

7.8-8.1 (multiple lines),

8.0 (single line) and 8.4-8.6 (multiple lines) of 7 value.

d. Mass spectra:

Peaks at 43 (CH CO), 61

(C H of M/e value.

Molecular weight is 222 (CH COOC H e. Refractive index:

EXAMPLES 2 6 The reaction was repeated in accordance with the process of Example 1, except using the starting materials and reaction conditions as stated in Table 1, wherein the symbols are as follows:

The results of the reaction of each example are shown in Table II, wherein each example number corresponds to those of Table l.

TABLE I1 AOD ADT Ex. Conver- Yield (g) n rate Yield (g) n rate D rate No. sion acetic acid EXAMPLE 7 0.2 m mole of palladium acetate, 0.074 mole of 2,7-dimethyl-l,3,7-octatriene and 0.05 mole of acetic acid were charged to a ml. microbomb, and then, 0.15 mole of butadiene was added with pressured nitrogen gas, and the contents were heated to C. The reaction was carried out at 110C. for 5 hours. After the reaction, the microbomb was cooled to room temperature, and unreacted butadiene was recovered.

According to analysis of the resulting products by gas chromatography, conversion of acetic acid was 26 percent, and the resulting products were 0.8 g. of lacetoxy-2,7-octadiene (l-AOD), 0.5 g. of 3-acetoxy- 1,7-octadiene (3-AOD), and 3-acetoxy-l,6-octadiene (3-AOD), 1.0 g. of 1-acetoxy-6,l 1-dimethyl-2,7,1 1- dodecatriene (l-ADT) and 0.4 g. of 3-acetoxy-6,1ldimethyl-1,7,1l-dodecatriene (3-ADT). Accordingly, the D rate was 48 percent, and the n rate of ADT was 71 percent.

EXAMPLE 8 0.1 m mole of palladium acetate, 0.1 mole of 1,3,7- octatriene and 0.05 mole of propionic acid were charged to a 100 ml. microbomb, and then 0.15 mole of butadiene was added with pressured nitrogen gas. The reaction was carried out at 110C. for 5 hours. After the reaction, the resulting products were analyzed in accordance with the process of Example 7.

The conversion of propionic acid was 24 percent and the resulting products were 0.65 g. of l-propionyloxy- 2,7-octadiene (l-AODO, 0.33 g. of 3-propionyloxy-l ,7- octadiene (3-AOD) and 3-propionyloxy-l,6-octadiene (3'-AOD), 1.18 g. of 1-propionyloxy-2,7,11- dodecatriene (l-ADT) and 0.38 g. of 3-propionyloxy- 1,7,1l-dodecatriene (3-ADT). Accordingly, the D rate was 55 percent and the n rate of ADT was 76 percent.

EXAMPLE 9 0.1 m mole of palladium acetate, 0.1 mole of 1,3,7- octatriene and 0.05 mole of benzoic acid were charged to a 100 ml. microbomb, and then 0.15 mole of butadiene was added with pressured nitrogen gas. The reaction was carried out at 1 10C. for 5 hours, and the resulting products were analyzed in accordance with the process of Example 7.

The conversion of benzoic acid was 21 percent, and the resulting products were 0.81 g. of l-benzoyloxy- 2,7-octadiene (l-AOD), 0.34 g. of 3-benzoyloxy-1,7- octadiene (3-AOD), and 3-ben zoyloxy-l ,6-octadiene (3'-AOD), 1.20 g. of 1-benzoy1oxy-2,7,1ldodecatriene (l-ADT) and 0.36 g. of 3-benzoyloxy- 1,7,11-dodecatriene (3-ADT). Accordingly, the D rate was 52 percent and the n rate of ADT was 77 percent.

EXAMPLE 10 0.1 m mole of palladium acetylacetonate was dissolved in 0.1 mole of 1,3,7-octatriene in a nitrogen gas atmosphere and the solution was charged with 0.05 mole of acetic acid in a 100 ml. microbomb. The microbomb was purged with nitrogen gas and 0.13 mole of butadiene was fed and the contents were heated to 110C. The reaction was carried out at 110C. for 5 hours. After the reaction, the microbomb was cooled to room temperature and unreacted butadiene was recovered.

According to analysis of the resulting products by gas chromatography, conversion of acetic acid was 61 percent and the resulting products were 1.35 g. of 1- acetoxy-2,7-octadiene (l-AOD), 0.45 g. of 3-acetoxy- 1,7-octadiene (3-AOD) and 3-acetoxy-1,6-ocatdiene l. A process for producing an acyloxydodecatriene which consists essentially of admixing and reacting 1,3,7-octatriene or a lower alkyl substituted 1,3,7- octatriene having the general formula:

Pd(acac),: palladium acetylacetonate Pd(OAc),: palladium acetate (3'-AOD), 2.96 g. of l-acetoxy-2,7,l l-dodecatriene and 1.34 g. of 3-acetoxy-l,7,l l-dodecatriene (3- R1 f ADT). Accordingly, the D rate was 64 percent, the n J; rate of AOD was 75 percent and the n rate of ADT was 69 percent. wherein each R may be the same or different and may i 10 be selected from the group consisting of hydrogen and EXAMPLE 11 a lower alkyl group; butadiene; and a carboxylic acid 0.04 m mole of palladium nitrate was dissolved in h vi tw t 20 carbon atoms and having the general 0.10 mole of 1,3,7-octatriene and 0.05 mole of acetic f rm l acid in a nitrogen gas atmosphere and the solution was charged to a 100 ml. microbomb. The microbomb was 15 RZCOZH purged with nitrogen gas and 0.248 mole of butadiene wh ein R is an alkyl group, a cycloalkyl group, an aryl was charged. The reaction was carried out at l 10C. group, or an lk group, i h presence f a Catefor 2 ou After the reaction, the microbomb was lytic amount of a catalyst consisting essentially of a dicooled to room temperature and unreacted butadiene valeht ll di compound l d f h group was recovered. consisting of organic acid salts of palladium (II), che- Aeeordihg to analysis of the resulting Products y gas late complexes of palladium (II) and palladium nitrate chromatography, eohversloh of acetic acid was 45 P wherein the molar ratio of the octatriene butadiene cent, and the resulting products were 0.78 g. of 1- eatboxyhc i i 0 0 5 5 0 1 1 aCetOXY'ZJ-OCtadieHe of 3'aeetoxy' 2. The process of claim 1, wherein said reaction is efl,7-octadiene (3-AOD) and 3-acetoxy-l,6-octadiene feeted at a temperature f 10 200 and a ptes (3-AOD), 2.93 g. of 1-acetoxy-l,7,l l-dodecatriene Sure f 1 50 atmospheres (l-ADT) and 0.56 g. of 3-acetoxy-1,7,l l-dodecatriene 3 The process f claim 1 wherein 1 X 1 I Accordingly, the D rate was 65 P the gram atom of divalent palladium component per mole rate of AOD was 55 Percent, and the rate of ADT of 1,3,7-octatriene or lower alkyl substitute is used as was 84 percent. the eatalyst EXAMPLES 12 l5 4. The process of claim 1, wherein l t acyloxydodecatriene or 3-acyloxydodecatr1ene 1s The reaction was earned out y adthhg either of added to the reaction mixture to cause the preferential acyloxy-2,7,l l-dodecatriene or 3-acyloxy-l,7,1lf ti f the opposite i dodecatriene to the reaction system. 6 g. of acetic acid, 5 T process f claim 1, wherein the cata|yst is 8- 0f 1,3,7-etatfiehe, of butadiene, cataladium acetate, palladium acetylacetonate, or pallalyst and either of 1-acyloxy-2,7,l l-dodecatriene or 3- h nitrate Y Y' JJ l'dodeeah'lehe were charged to a 100 6. The process of claim 1, wherein the carboxylic autoclave yp and the reaction was Carried acid is acetic acid, propionic acid or benzoic acid. out at 100C. for 5 hours. After the reaction, unreacted 40 7, Th process f l i 1, h i 1 3 7 i butadiene was recovered, and the resulting pl'oduets butadiene and acetic acid are reacted in a molar ratio were amllyzed y gas Chromatography of 1.0 0.5 5.0 0.1-10 at 40-120c. in the presence The reaction eohditloh and results are Show" of a catalyst of a divalent palladium compound selected Table from the group consisting of organic salts of palladium Having how fully described the invention it will be (ll), chelate complexes of palladium (II) and palladium pp to one of Ordinary in the art that y nitrate, and acetoxydodecatrienes are recovered from changes and modifications can be made thereto withh reaction product out departing from the spirit or scope of the invention. 8 Th process f l i 7, h i h catalyst i what is claimed as new and desired to be Secured y ladium acetyl acetonate, palladium acetate or palla- Letters Patent is: so dium nitrate.

TABLE III Catalyst Additive Products (g) Formed Products Ex. No. type g. type g. AOD 3-ADT l-ADT D(;a;e 3-ADT l-ADT Formed7 D rate 12 Pd(acac) 0.03 4.9 1.8 4.0 69 1.3 4.0 69 13 0.03 3-ADT 1 7 3.5 1.8 4.9 73 0.1 4.9 98 14 0.03 l-ADT 2.4 5.7 2.4 6.6 73 2.4 4.2 64 15 PKKOAC), 0.02 3-ADT 1 5 2.7 1.5 3.5 0 3.5 100 Formed product (newly formed product): Amount of the product reduced y the amount of additive Formed D rate: D rate based on the newly fonned product of 1,3,7-octatriene is used as the catalyst.

10. The

process of claim 7,

wherein aceloxydodecatriene or 3-acyloxydodecatriene added to the reaction mixture to cause the preferential formation of the opposite isomer. 

2. The process of claim 1, wherein said reaction is effected at a temperature of 10*C. - 200*C. and a pressure of 1 - 50 atmospheres.
 3. The process of claim 1, wherein 1 X 10 4 - 1.0 gram atom of divalent palladium component per mole of 1,3,7-octatriene or lower alkyl substitute is used as the catalyst.
 4. The process of claim 1, wherein 1-acyloxydodecatriene or 3-acyloxydodecatriene is added to the reaction mixture to cause the preferential formation of the opposite isomer.
 5. The process of claim 1, wherein the catalyst is palladium acetate, palladium acetylacetonate, or palladium nitrate.
 6. The process of claim 1, wherein the carboxylic acid is acetic acid, propionic acid or benzoic acid.
 7. The process of claim 1, wherein 1,3,7-octatriene, butadiene and acetic acid are reacted in a molar ratio of 1.0 : 0.5-5.0 : 0.1-10 at 40-120*C. in the presence of a catalyst of a divalent palladium compound selected from the group consisting of organic salts of palladium (II), chelate complexes of palladium (II) and palladium nitrate, and acetoxydodecatrienes are recovered from the reaction product.
 8. The process of claim 7, wherein the catalyst is palladium acetyl acetonate, palladium acetate or palladium nitrate.
 9. The process of claim 7, wherein 1 X 10 4 - 1.0 gram atom of divalent palladium component per mole of 1,3,7-octatriene is used as the catalyst.
 10. The process of claim 7, wherein 1-aceloxydodecatriene or 3-acyloxydodecatriene is added to the reaction mixture to cause the preferential formation of the opposite isomer. 